CN108948374A - A kind of lignite utilizes method - Google Patents
A kind of lignite utilizes method Download PDFInfo
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- CN108948374A CN108948374A CN201810970462.4A CN201810970462A CN108948374A CN 108948374 A CN108948374 A CN 108948374A CN 201810970462 A CN201810970462 A CN 201810970462A CN 108948374 A CN108948374 A CN 108948374A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Abstract
A kind of lignite utilizes method, and the present invention relates to a kind of lignite to utilize field, and in particular to a kind of using lignite is raw material extraction humic acid method field.Raw material of the present invention is gone out through strong acid reverse process the impurity in raw material in lignite processing system, into alkali pool processing system alkali carries humic acid, poly-aluminium is added into the humic acid solution of alkali carries, it flocculates, humic acid collectively constitutes flocculate with aluminium ion and separates with lye, flocculate enters sour pond processing system, and lye returns to alkali pool system circulation and uses.
Description
Technical field
The present invention relates to a kind of lignite to utilize method field, and in particular to a kind of side that humic acid is extracted using lignite as raw material
Method field.
Background technique
Lignite is the minimum pit coal of degree of coalification, is not easy storage and remote fortune, and when burning is serious to air pollution.However it is brown
But contain a large amount of humic acid and fulvic acid in coal；Humic acid content accounts for the 80% of its organic matter in the lignite of part.In recent years, rotten
Phytic acid is widely used in multiple industries because of its unique physicochemical property, therefore using lignite as raw material, has extracted humic acid
Hot spot as related fields research.
The humic acid method extracted from lignite in research at present is mainly " alkali carries acid out ", is extracted under alkaline condition brown
Then humic acid in coal is adjusted to highly acid, humic acid is precipitated.Outstanding problem existing for this method is concentrated mainly on following
Two aspects:
The first, " alkali carries acid out " soda acid dosage is big, and environmental pollution is serious.
The pH value of lye when lignite extracts is typically larger than 10, and precipitation process then needs stronger acid condition, by strong
Alkali environment is transferred to strong acid environment, to consume a large amount of acid, and these soda acids are generally difficult to be recycled.
The second, lignite component difference is big, and corresponding extraction process is difficult to meet the requirement of humic acid actual extracting.
Due to the difference of the degree of coalification of lignite, there is also very big difference for the content of humic acid；Even same area
The lignite of domain different coal, there are biggish differences for ingredient.Therefore for lignite extract humic acid technique and equipment aspect all
There should be corresponding " compatibility ", to adapt to the difference of raw material.This is very important the extraction of natural products.
Such as in lye extraction process, humic acid content is low to will cause lye residue, and remaining lye not only wastes, and
A large amount of acid are needed to go to neutralize；It is insufficient that humic acid content height will cause rotten plant extraction.Prior art is using in extraction process
PH is monitored, control pH is not less than 10, actually to improve extraction effect, keeps lye superfluous.
Summary of the invention
Based on above-mentioned technical problem, the present invention proposes following inventive concept
Design 1: soda acid usage amount is reduced
1, poly-aluminium is added into the humic acid solution of extraction, flocculates, corruption is planted it is not necessary that entire solution is adjusted to acidity after alkali carries
Acid collectively constitutes flocculate with aluminium element and separates with lye, and lye return system can be recycled.
2, the precondition that lye is recycled is that lye should be clean.The present invention is first is that lignite passes through pretreatment, as
Processing of the acid solution to lignite guarantees introducing impurity as few as possible in lye from raw material level；Second is that poly-aluminium is flocculated, inherently
For the purification process of lye.
3, acid solution is used for multiple times: as shown in Fig. 1-C, in acid condition, flocculated state is destroyed flocculate, aluminium with from
Sub- form enters in solution, and humic acid is precipitated with precipitation form.Part acid solution in the acid solution of this part is as lignite pretreatment liquid
Acid solution is purified with aluminium hydroxide.
4, compared with prior art；Present invention introduces poly-aluminiums as flocculant, but poly-aluminium is the byproduct in the present invention, nothing
It need to additionally introduce, and can recycling with aluminium element.
Design 2: the reverse mass transfer of solid-liquid
During lignite extracts aluminum ions, acid solution is advanced from left to right；Lignite is advanced from right to left；The two is inversely advanced.
Reverse mass transfer the utility model has the advantages that
(1) meet extraction process requirement.Acid used is extracted with the progress of extraction, sour intensity acid can gradually weaken, solid-liquid
The intensity of reverse mass transport process acid can gradually weaken along direction of travel；The extraction difficulty of lignite intermediate ion can be along direction of travel
It gradually increases.During existing actual extracting: when starting, substance to be extracted is easy to extract, with the progress of extraction, later period acid
Concentration it is low, but substance to be extracted is difficult to extract.Therefore the reverse mass transfer of solid-liquid is the effective ways for solving the problems, such as this.
(2) " compatibility " for improving production technology realizes continuous production, easily controllable.Due to the difference of lignite ingredient, mention
Be difficult to during taking configure corresponding suitable number of acid solution for the raw material of different content, this problem in continuous production especially
It is prominent.
(3) the prominent advantage of reverse mass transfer shows " total amount maintains an equal level, and part is excessive ": firstly, reaction-ure mixture with it is existing
Technique dosage maintains an equal level: it is 1 that the mark that fully reacting is finally reached during said extracted, which is the pH of exit solution of lignite, i.e.,
Lignite passes through the processing of strong acid, and lignite can be kept to pass through the processing of strong acid by addition acid solution；The mark of corresponding acid solution
Will is that the exit pH value of solution of acid solution is 4, this can be realized by adjusting the additive amount of lignite.Secondly, reactant part mistake
Amount: in the reaction process of lignite, it is obvious excess during final reaction, ensure that the abundant progress of reaction.
The above inventive concept is realized by technical solution in detail below.A kind of method that lignite utilizes includes at lignite
Reason system, alkali pool processing system, sour pond processing system and four part of separate tank processing system composition.
First part: lignite processing system:
Equipment:
It is formed as shown in Fig. 2, lignite processing unit (1) is sequentially connected by 7 the first process chambers (1-1), the first process chamber (1-1)
Left end is equipped with the first grid (1-2)；4-8 the first agitating paddles (1-6) are equipped in first process chamber (1-1)；On the right side of process chamber
The first inlet tube of top (1-10), the first inlet tube (1-10) pass through the first liquid feed valve (1-8) and the first gathering tube (1-12) phase
Connection；The first leakage fluid dram (1-7), the first leakage fluid dram (1-7) are connected with the first drain pipe (1-3) below first grid (1-2),
First drain pipe (1-3) is connected by the first liquid valve (1-4) with the first gathering tube (1-12), and the first drain pipe (1-3) is logical
The second liquid valve (1-5) is crossed to be connected with the second gathering tube (1-11)；Spaced valve (1-9) on first gathering tube (1-12) is located at
Between adjacent 2 the first process chambers (1-1)；As shown in fig. 6, the first grid (1-2) of the first process chamber of the leftmost side (1-1) passes through
First material conveyer belt (1-14) is connected with the first centrifuge (1-13)；4 paddles are uniformly distributed on first agitating paddle (1-6)
Piece (1-61), stirring blade (1-61) outside connect 2 caudas (1-62), the folder between stirring blade (1-61) and cauda (1-62)
Angle is 120 degree, and the angle between two caudas (1-62) is 120 degree.
Technique:
Lignite is advanced by No. 1 process chamber to No. 7 process chamber directions, and is spaced a process chamber and material is added；Initial acid solution A1 is by 7
Number process chamber is advanced to No. 1 process chamber direction, and is spaced a process chamber and material is added；Lignite passes through n-1 process chamber first
Grid (1-2) enters n process chamber, and acid solution enters n process chamber by the first inlet tube (1-10), at the first agitating paddle (1-6)
Extracted under stirring action, after extraction starting the first grid (1-2) simultaneously acid solution by the first leakage fluid dram (1-3) be discharged again by
First inlet tube (1-10) enters n process chamber, forms circulation in acid solution, when lignite passes through the first grid of n process chamber (1-2)
Into after n+1 process chamber, acid solution is entered by the first leakage fluid dram (1-3) into the first gathering tube (1-12) in n process chamber
N-1 process chamber enters the first centrifuge (1-13) after lignite passes through No. 7 process chambers, and solid A enters first after centrifuge separation
In alkali pool (2-1)；When acid solution pH value is greater than 4, by the second gathering tube (1-11), being labeled as W, W enters separate tank processing
In system (4).
Technology illustrates 1-1: reverse mass transfer in extraction process, as described in inventive concept 2, details are not described herein.
Technology illustrates 1-2: acid solution used by this step is studied is the acid solution in sour pond, and the main function in sour pond is to slough
Aluminium ion in flocculate, ingredient are the acid solutions containing aluminium ion pH=1-2, and extracting using the part solution can be abundant
Extract fulvic acid, while in lignite there is it is a certain number of be easy to extract aluminium salts, using hydrochloric acid may be implemented for aluminium from
The extraction of son, raw material of the aluminium ion extracted as preparation polychlorostyrene.
Technology illustrates 1-3: the effect of the first agitating paddle (1-6) is to guarantee sufficiently connecing for lignite and acid solution during the extraction process
Touching and the displacement for realizing solid material horizontal direction.Cauda (1-62), can be by underlying solid " shovel " at bottom
It rises, the solid being clipped between two the first agitating paddles (1-6), the first of lower section during falling in company with two the first agitating paddles
The cauda (1-62) of agitating paddle (1-6) can change the direction of solid whereabouts, so that it is fallen forwards, into next agitating paddle
Range is stirred, is to realize the movement of horizontal direction under the cooperation of fluent solution.
Technology illustrates 1-4: the reverse mass transfer of solid-liquid, solves the technical problem of aluminium extracted in separation process.When pH value is
When 3-5, aluminium ion is precipitated from solution with precipitation form, this pH value range is big, it is difficult to select suitable pH value for lignite
It is separated with extracting solution.
Using traditional handicraft, lignite is carried out when selective extraction liquid is in lower ph and extracting solution is separated, such as pH=
Acid solution will be extracted when 3 to separate with lignite, extraction acid solution is adjusted to pH value can be such that the aluminium in solution is sufficiently recycled greater than 5,
But acid solution of the pH greater than 3 has neither part nor lot in and extracts to lignite, and needs to adjust pH, additionally consumes lye.
If pH value is higher, extracting solution is separated when such as pH=4-5 with lignite, is adjusted to pH value greater than 5 although disappearing
The alkali number of consumption is less, and acid solution utilization is more abundant, but aluminum hydroxide precipitation has been produced when pH=3-4, the aluminium hydroxide of precipitating
It is mixed with lignite, is difficult to dissolve in alkali pool extraction process, be eventually discharged, can not recycle in company with filter residue.
Acid used by this invention expects reversed mode, solves the above problem, selects to isolate solution when pH=4
Come, acid solution utilization is more abundant, while the aluminium hydroxide being settled out in pH=3-4 with lignite it is mobile, the acid of the acid solution contacted
Property gradually increase aluminium atom and re-dissolve into extracting solution, as acid solution movement carries out above-mentioned precipitation process again, realize aluminium
Be sufficiently separated.
Second part alkali pool processing system
Equipment:
As shown in figure 3, alkali pool system (2) is divided into the first alkali pool (2-1) and the second alkali pool (2-11)；First alkali pool (2-1) and
First pipe (2-10), changeable the first surge tank (2-21) and the second surge tank (2- in parallel are equipped between two alkali pools (2-11)
22)；The second leakage fluid dram (2-13) of second alkali pool (2-11) is connect with the one end second pipe (2-15), and second pipe (2-15) is another
One end is connect with the first decanter centrifuge (2-16), and the first decanter centrifuge (2-16) passes through third pipeline (2-17) and the first alkali
Pond (2-1) is connected；
One end of first alkali pool (2-1) is highest point (2-4), and highest point (2-4) to minimum point (2-5) is identical by 20-100 grades
Ladder (2-6) connection, it is single on the outside of solarization air cap (2-7) that each ladder (2-6) is interior, which to have 3-5 identical solarization air caps (2-7),
To valve (2-8)；The second grid bottom (2-2) is located at the plane where minimum point (2-5), at minimum point (2-5) on side wall
Have the second leakage fluid dram (2-9), the first surge tank (2-21) and are connected between the second leakage fluid dram (2-9) and first pipe (2-10)
Two surge tanks (2-22)；The third grid bottom end (2-3) is located at highest point (2-4) institute in the plane；It is above third grid (2-3)
Second inlet tube (2-18)；Adjacent first ladder (2-6) top of plane (2-4) where highest point is feed points (2-19)；
Feed points (2-19) middle side part is equipped with the 6th pH value on-line control device (2-30) in first alkali pool (2-1)；
The one end second alkali pool (2-11) has the second leakage fluid dram (2-13), has subregion plate (2- at the second leakage fluid dram (2-13)
It 12), is first pipe (2-10) nozzle and poly-aluminium feed pipe (2-25) nozzle above the second alkali pool (2-11)；Second alkali pool (2-
11) equipped with 4-8 the second agitating paddles (2-14), the second leakage fluid dram (2-13) connects second pipe (2-15), second pipe (2-
15) the first pump (2-20) is installed on and provides power for flocculated mixture advance, second pipe (2-15) other end and first crouch
The feed inlet of screw centrifuge (2-16) is connected；First decanter centrifuge (2-16) liquid outlet passes through third pipeline (2-17) and second
Inlet tube (2-18) is connected；The solid material that first decanter centrifuge (2-16) is isolated enters No. 1 second of sour cell system (3)
In process chamber (3-1)；
It is equipped with 4-8 the first on-line pH value regulating devices (2-24) in second alkali pool (2-11), adjusts in the second alkali pool (2-11)
PH value is equipped with the second pH value on-line control device (2-23) between 10.0-11.0 in third pipeline (2-17), adjust pH value
Between 11.0-11.5；
First alkali pool (2-1) is designed using ramp type, and slope angle with horizontal plane is 5-30 degree.
Technique:
After centrifuge separation solid A by feed points (2-19) enter the first alkali pool (2-1) in, lye aeration and gravity it is common
It is mobile to the second grid (2-2) under effect, and realized and be separated by solid-liquid separation by the second grid (2-2), solid is the lignite after extracting
Waste residue B, liquid are the second extracting solution C containing humic acid, and the second extracting solution C enters the first surge tank (2-21), as extracting solution C
When volume is the 80% of the first surge tank (2-21), the second extracting solution C enters the second surge tank (2-22), the first surge tank (2-
21) sampling carries out flocculation detection, and extracting solution C is put into the second alkali pool (2-11) in the first surge tank (2-21)；First surge tank
(2-21) and the second surge tank (2-22) alternately carry the second extracting solution C, are put into the second alkali pool (2-11), mention after sample detection
Concentration, which is added, according to the ratio that 0.05-0.5 grams of poly-aluminium is added in every gram of humic acid during taking liquid to be put into the second alkali pool (2-11) is
The poly-aluminium solution of 1-10g/L, humic acid enter the second alkali pool (2-11) in the form of flocculate by first pipe (2-10) nozzle
It is 10-300 minutes by the second leakage fluid dram (2-13) discharge time used, by the first decanter centrifuge (2-16) after flocculation
It is separated by solid-liquid separation, solid is flocculate D, and liquid is lye E；Lye E passes through third pipeline (2-17) and the second inlet tube (2-18)
It returns the first alkali pool (2-1), is recycled, feed points (2-19) middle side part is equipped with the 6th online pH in the first alkali pool (2-1)
Value adjusting device (2-30) adjusts pH value between 10.5-11.0；The second on-line pH value tune is equipped in third pipeline (2-17)
Regulating device (2-23) adjusts pH value between 11.0-11.5.
Technology illustrates 2-1: in the industrial production of this step, the maximum problem faced is the object in continuous production process
Material proportion is unable to control, and is caused poly-aluminium superfluous or is flocculated incomplete.The inventive concept of this step remains: being matched with circulation adjustment reaction
Than improving the compatibility of industrial manufacture process.
If sodium humate is excessive in solution, remaining humic acid can be recycled back to flocculate next time as extracting solution participation；
If poly-aluminium is excessive, residual Al enters dealuminzation device (3), further reuse, the raw material as preparation poly-aluminium.It is most closed in this step
The technical controlling point of key is to guarantee that superfluous aluminium ion does not dissolve (pH value is higher than 12) in alkali pool (2-11), returns to the first alkali pool
(2-1) is precipitated, and is discharged with lignite waste residue B.Therefore pH value control area and numerical value are important control point.Using slope flow model
Design function: 1) continuous extract is realized；2) the pH value control of multiple spot multizone may be implemented；3) class pipeline type designs.
Technology illustrates 2-2: showing mixed solution the mentioning for humic acid of sodium carbonate and sodium hydroxide by previous experiments
Effect is taken to be higher than simple sodium carbonate and sodium hydroxide.Therefore, present study be passed through carbon dioxide benefit it is as follows: 1), improve
The extraction efficiency of humic acid.2) the abundant dissolution to humic acid, is realized by the gradient of air-flow promotion and alkali pool.3), sodium carbonate
The dissolution of calcium ions and magnesium ions in extraction process can effectively be controlled.
Technology illustrates 2-3: it is that alkali acid conversion consumption is largely sour that humic acid alkali carries acid out, which extracts most important problem, at present
Liquid, while there are a large amount of chloride ions in mother liquor, it is difficult to it is effectively treated.In the present invention by the way that experimental results demonstrate in alkali
Property solution (pH value 11) when, suitable poly-aluminium is added, can realize that humic acid flocculate from lye and come out by flocculation mode,
It is separated with lye, it is not necessary to adjust solution as acidity, reduce the consumption of a large amount of acid solutions.
Technology illustrates 2-4: this item extraction process is extracted using on-line pH value regulative mode, it is possible to prevente effectively from highly basic
Destruction for humic acid bioactivity.Throughout the extraction process, pH value can not only reduce the dissolution of silicon less than 11.5, but also
It can be to avoid the loss that aluminium in flocculation process is added.In flocculation process, if aluminium ion is excessive, pH value can be generated higher than 12 can
Dissolubility meta-aluminate is returned after dissolution in the first alkali pool (2-1), and pH value decline generates aluminium hydroxide again, after centrifuge separation
It is removed in company with solid filter residue, causes unnecessary loss.
Part III acid cell system
Equipment:
As shown in figure 4, sour cell system (3) is sequentially connected by 4 second processing rooms (3-1) and is formed, number consecutively is No. 1-4, the
Two process chambers (3-1) right end is equipped with the 4th grid (3-2), and the 4th grid lower end (3-2) is connected with third conveyer belt (3-11)；
2-4 third agitating paddle (3-3) is equipped in second processing room (3-1)；The 4th grid (3-2) in No. 4 second processing rooms (3-1)
Discharge port is connected by second material conveyer belt (3-4) with the feed inlet of the second decanter centrifuge (3-5)；2-4 second processing
Room (3-1) is designed with fluid level control device (3-6)；When liquid level declines in n second processing room (3-1), fluid level control device
(3-6) adds to the solution chosen in concentrated acid and n-1 second processing room (3-1) in proportion in n second processing room (3-1),
Keep the volume and pH value of solution in n second processing room (3-1)；When liquid level declines in No. 1 second processing room (3-1), liquid level
Control device (3-6) adds to the solution chosen in washing lotion tank (3-7) in proportion and water in No. 1 second processing room (3-1), protects
Hold the volume and pH value of solution in No. 1 second processing room (3-1)；
The liquid circulation that second decanter centrifuge (3-5) liquid outlet comes out returns to No. 4 second processing rooms (3-1), solid alternately into
Enter in the first cleaning-drying tank (3-8) or the second cleaning-drying tank (3-9), the first cleaning-drying tank (3-8) or the second cleaning are dry
Dry tank (3-9) washing lotion outlet is connected with washing lotion tank (3-7) by pipeline；No. 4 second processing rooms bottom (3-1) is equipped with and takes sour mouth
(3-10).
Technique:
Flocculate enters in sour cell system (3), and the pH value of acid solution is respectively 6,4,2,1 in 1-4 second processing room (3-1), wadding
Condensate is moved by solution flowing and the 4th grid (3-2), successively from No. 1 second processing room (3-1) to No. 4 second processing rooms
(3-1) movement, is centrifugated, and cleaned with clear water to neutrality, then after alcohol is washed, 80 by the second decanter centrifuge (3-5)
DEG C dry 2-6 hours；
In No. 4 second processing rooms (3-1) after acid liquor filtering, as acid solution A1 initial in lignite processing system；No. 3 second processing rooms
Enter in No. 4 second processing rooms (3-1) after acid liquor filtering and after concentrated hydrochloric acid mixing in (3-1), keeps No. 4 second processing room (3-
1) stabilization of pH value and volume；Enter No. n+1 second after acid liquor filtering and after concentrated hydrochloric acid mixing in n second processing room (3-1)
In process chamber (3-1)；Enter in No. 1 second processing room (3-1) after washing lotion and concentrated hydrochloric acid mixing in washing lotion tank (3-7).
Technology illustrates 3-1: although flocculate, which is directly added into strong acid, can achieve the aluminum ions effect of removal, quickly
Soda acid variation, will affect the activity of humic acid, will lead to eluent by the way of simple gradient elution and be difficult to abundant benefit
With, and it will appear floccule body and be destroyed, the phenomenon that part humic acid dissolution is pulled away with eluent.Therefore this step is adopted
With the method for grad enhancement acidity, the solid transmitting in the same direction of liquid can make the humic acid of dissolution finally obtain recycling.
Technology illustrates 3-2: since humic acid flocculation process has catharsis, flocculate dissociation process for water body
In have impurity and be discharged into acid solution, acid solution can be used for multiple times, but need to constantly update, and the acid solution of update is as extracting solution.
Part IV: separate tank processing system
Equipment:
As shown in figure 5, separate tank processing system (4) is equipped with the knockout drum (4-1) and one of filter plate by poly-aluminium synthesis tank, two bottoms
A third process chamber (4-3) composition；Knockout drum (4-1) and third process chamber (4-3) are connected by rapid mixing chamber (4-2)；
First charging aperture (4-11) at the top of knockout drum (4-1) is connected with the second gathering tube (1-11)；At the top of knockout drum (4-1)
Second charging aperture (4-12) connect with acid tube (3-10) is taken by pipeline, the 3rd pH regulation device is equipped in knockout drum (4-1)
(4-13)；
The 4th online pH regulation device (4-21), agitating device (4-22) and ultrasonic mixing dress are equipped in rapid mixing chamber (4-2)
Set (4-23)；
Third process chamber is diagonally divided into two parts by the 5th grid (4-31) in third process chamber (4-3), at third
It manages and is equipped with the 5th pH regulation device (4-32) in room (4-3).
Technique:
Acid solution W of the pH value greater than 4 enters in knockout drum (4-1), adjusts pH=7 of solution, is separated by filtration, and liquid Y is that fulvic acid is molten
Liquid；The acid solution in No. 4 second processing rooms (3-1) is added to knockout drum (4-1), until pH value of solution≤3, are put into quick mixing for solution
In slot (4-2), solution is in the 4th online pH regulation device (4-21), agitating device (4-22) and ultrasonic mixing device (4-23)
Under effect, after quickly adjusting pH=7, into third process chamber (4-3), solid aluminum hydroxide is divided by the 5th grid (4-31)
From solution produces the raw material of fulvic acid by being incorporated as after the multiple circulating filtration of the circulatory system with solution Y；
Aluminium hydroxide is added in 4mol/L hydrochloric acid the ratio for being 10:1-5:1 according to the molar ratio of hydrochloric acid and aluminium hydroxide,
110 DEG C stirring 3-5 hours, a small amount of aluminium powder is added to solution no longer vigorous reaction, 90 DEG C of adjusting PH to 4.5, after staticly settling again
Filtering obtains polymeric aluminum chlorides solution, adjusts concentration, and the humic acid that flocculates is added in the second alkali pool (2-11).
Technology illustrates that 4-1 aluminum hydroxide precipitation can adsorb the substances such as 3 acid in corresponding richness in the process, needs to purify ability
Guarantee the product quality of poly-aluminium.
After solution is put into rapid mixing chamber (4-2), by quickly stirring, the aluminium hydroxide that the operations such as ultrasound ensure to generate
It is separated as early as possible, adsorption bridging, net is avoided to catch phenomena such as volume is swept, avoid the generation of flocculation phenomenon.
The utility model has the advantages that
1, it is not necessarily to entire solution being adjusted to acidity after alkali carries, poly-aluminium is added in the humic acid solution of extraction, flocculates, humic acid
It collectively constitutes flocculate with aluminium element to separate with lye, lye can be recycled.
2, the separation of humic acid and lye can be thus achieved in poly-aluminium flocculation, and is the purification process for lye.
3, byproduct of the poly-aluminium in present study, and can recycling with aluminium element.
4, " compatibility " of production technology is improved, realizes continuous production, it is easily controllable.
Figure of description:
Attached drawing 1: process flow chart A；Aluminium element circulation figure B；Soda acid moves towards figure C.
Attached drawing 2: lignite processing system side elevational cross-section Local map A；Lignite processing system top view B；Lignite processing system bottom
View C, the first agitating paddle (1-6) enlarged drawing D.
Attached drawing 3: alkali pool processing system schematic diagram A；First alkali pool (2-1) top view B；Second alkali pool (2-11) top view C；
First alkali pool (2-1) is along auxiliary line AA sectional view D；First alkali pool (2-1) is along auxiliary line AA section partial enlarged view E.
Attached drawing 4: sour cell system side elevational cross-section Local map A；Second material conveyer belt (3-4) and the second decanter centrifuge (3-
5) partial schematic diagram B；It is cleaned and dried tank part partial schematic diagram C.
Attached drawing 5: enter lignite processing equipment figure before alkali pool.
Attached drawing 6: lignite processing system Local map.
In figure: 1: lignite processing unit；1-1: the first process chamber；1-2: the first grid；1-3: the first drain pipe；1-4: the
One liquid valve；1-5: the second liquid valve；1-6: the first agitating paddle；1-7: the first leakage fluid dram；1-8: the first liquid feed valve；1-9: interval
Valve；1-10: the first inlet tube；1-11: the second gathering tube；1-12: the first gathering tube；1-13: the first centrifuge；1-14: the first
Material conveyor belt；1-61: stirring blade；1-62: cauda；
2: alkali pool processing system；2-1: the first alkali pool；2-2: the second grid；2-3: third grid；2-4: highest point；2-5: minimum
Point；2-6: ladder；2-7: solarization air cap；2-8: one-way cock；2-9: the second leakage fluid dram；2-10: first pipe；2-11: the second alkali
Pond；2-12: subregion plate；2-13: the second leakage fluid dram；The second agitating paddle of 2-14；2-15: second pipe；2-16: the first sleeping spiral shell centrifugation
Machine；2-17: third pipeline；2-18: the second inlet tube；2-19: feed points；2-20: the first pump；2-21: the first surge tank；2-
22: the second surge tanks；2-23: the second on-line pH value regulating device；2-24: the first on-line pH value regulating device；2-25: poly-aluminium into
Expects pipe；2-30: the six on-line pH value regulating device；
3: sour cell system；3-1: second processing room；3-2: the four grid；3-3: third agitating paddle；3-4: second material conveyer belt；
3-5: the second decanter centrifuge；3-6: fluid level control device；3-7: washing lotion tank；3-8: the first is cleaned and dried tank；3-9: the second is clear
Wash drying chamber；3-10: sour mouth is taken；3-11: third conveyer belt；
4: separate tank processing system: 4-1: knockout drum；4-2: rapid mixing chamber；4-3: third process chamber；4-11: the first charging
Mouthful；4-12: second charging aperture；4-13: the online pH regulation device of third；4-21: the four online pH regulation device；4-22: stirring
Device；4-23: ultrasonic mixing device；4-31: the five grid；4-32: the five online pH regulation device.
Specific embodiment:
Embodiment 1
A kind of lignite utilizes method, comprising the following steps:
Step 1: lignite is advanced by No. 1 process chamber to No. 7 process chamber directions, and is spaced a process chamber and material is added；Initial acid
Liquid A1 is advanced from No. 7 process chambers to No. 1 process chamber direction, and one, material interval process chamber is added；Lignite passes through No. n-1 processing
The first grid of room (1-2) enters n process chamber, and acid solution enters n process chamber by the first inlet tube (1-10), in the first agitating paddle
Extracted under (1-6) stirring action, after extraction starting the first grid (1-2) simultaneously acid solution by the first leakage fluid dram (1-3) arrange
N process chamber is entered by the first inlet tube (1-10) again out, forms circulation in acid solution, when lignite passes through the first lattice of n process chamber
After grid (1-2) enter n+1 process chamber, acid solution enters the first gathering tube (1- by the first leakage fluid dram (1-3) in n process chamber
12) enter n-1 process chamber, enter the first centrifuge (1-13) after lignite passes through No. 7 process chambers, solid A after centrifuge separation
Into in the first alkali pool (2-1)；When acid solution pH value is greater than 4, by being labeled as material W, material in the second gathering tube (1-11)
W enters in separate tank processing system (4).
Step 2: after centrifuge separation solid A by feed points (2-19) enter the first alkali pool (2-1) in, lye aeration and
It is mobile to the second grid (2-2) under the collective effect of gravity, and realized and be separated by solid-liquid separation by the second grid (2-2), solid is to mention
Lignite waste residue B after taking, liquid are that the second extracting solution C, the second extracting solution C containing humic acid enters the first surge tank (2-
21), when extracting solution C volume is the 80% of the first surge tank (2-21), the second extracting solution C enters the second surge tank (2-22), the
One surge tank (2-21) sampling carries out flocculation detection, and extracting solution C is put into the second alkali pool (2-11) in the first surge tank (2-21),
Poly-aluminium solution is added simultaneously, the molal quantity that poly-aluminium solution is added is that poly-aluminium molal quantity is added needed for calculating according to testing result
80%；First surge tank (2-21) and the second surge tank (2-22) alternately carry the second extracting solution C, are put into second after sample detection
In alkali pool (2-11), while it is the poly- of 1-10g/L that concentration, which is added, according to the ratio that 0.05-0.5 grams of poly-aluminium is added in every gram of humic acid
Aluminum solutions, humic acid by first pipe (2-10) nozzle enter the second alkali pool (2-11) in the form of flocculate by the second leakage fluid dram
(2-13) discharge time used is 10-300 minutes, is separated by solid-liquid separation after flocculation by the first decanter centrifuge (2-16), solid
For flocculate D, liquid is lye E；Lye E returns to the first alkali pool by third pipeline (2-17) and the second inlet tube (2-18)
(2-1) is recycled, and feed points (2-19) middle side part is equipped with the 6th on-line pH value regulating device (2- in the first alkali pool (2-1)
30) pH value, is adjusted between 10.5-11.0；The second on-line pH value regulating device (2-23) is equipped in third pipeline (2-17),
PH value is adjusted between 11.0-11.5；
Step 3: flocculate enters in sour cell system (3), in 1-4 second processing room (3-1) pH value of acid solution be respectively 6,4,
2, flocculate is flowed by solution and the 4th grid (3-2) moves, successively from No. 1 second processing room (3-1) to No. 4 second processings
Room (3-1) movement, is centrifugated, and clear water is cleaned to neutrality, alcohol is washed, 80 DEG C of dry 2-6 by the second decanter centrifuge (3-5)
Hour；In No. 4 second processing rooms (3-1) after acid liquor filtering, as acid solution A1 initial in lignite processing system；No. 3 second processings
Enter in No. 4 second processing rooms (3-1) after acid liquor filtering and after concentrated hydrochloric acid mixing in room (3-1), keeps No. 4 second processing rooms
The stabilization of (3-1) pH value and volume；Enter No. n+1 the in n second processing room (3-1) after acid liquor filtering and after concentrated hydrochloric acid mixing
In two process chambers (3-1)；Enter in No. 1 second processing room (3-1) after washing lotion and concentrated hydrochloric acid mixing in washing lotion tank (3-7)；
Acid solution W of the step 4:pH value greater than 4 enters in knockout drum (4-1), adjusts pH=7 of solution, is separated by filtration, and liquid Y is richness
In acid solution；The acid solution in No. 4 second processing rooms (3-1) is added to knockout drum (4-1), until pH value of solution≤3, solution is put into fastly
In fast mixing channel (4-2), solution is in the 4th online pH regulation device (4-21), agitating device (4-22) and ultrasonic mixing device
Under the action of (4-23), after quickly adjusting pH=7, into third process chamber (4-3), by the 5th grid (4-31) by solid hydrogen
Aluminium oxide separation, solution produce the raw material of fulvic acid by being incorporated as after the multiple circulating filtration of the circulatory system with solution Y；
Aluminium hydroxide is added in 4mol/L hydrochloric acid the ratio for being 10:1-5:1 according to the molar ratio of hydrochloric acid and aluminium hydroxide,
110 DEG C stirring 3-5 hours, a small amount of aluminium powder is added to solution no longer vigorous reaction, 90 DEG C of adjusting PH to 4.5, after staticly settling again
Filtering obtains polymeric aluminum chlorides solution, adjusts concentration, and the humic acid that flocculates is added in the second alkali pool (2-11).
Embodiment 2
A kind of lignite utilizes method, and the present embodiment is substantially the same manner as Example 1, the difference is that: according to every gram in step 2
The ratio that 0.05-0.5 grams of poly-aluminium is added in humic acid is added the poly-aluminium solution that concentration is 1-10g/L and preferably plants according to every gram of corruption
The poly-aluminium that concentration is 1g/L is added in the ratio that 0.05 gram of poly-aluminium is added in acid.
Technology explanation: having part humic acid and do not flocculate, but can return to flocculation again and extract；The utilization rate of poly-aluminium
It is high.
Embodiment 3
A kind of lignite utilizes method, and the present embodiment is substantially the same manner as Example 1, the difference is that: according to every gram in step 2
The ratio that 0.05-0.5 grams of poly-aluminium is added in humic acid is added the poly-aluminium solution that concentration is 1-10g/L and preferably plants according to every gram of corruption
The poly-aluminium that concentration is 10g/L is added in the ratio that 0.5 gram of poly-aluminium is added in acid.
Technology explanation: the utilization rate of poly-aluminium is relatively low, and humic acid flocculation is complete.
Embodiment 4
A kind of lignite utilizes method, and the present embodiment is substantially the same manner as Example 1, the difference is that: according to every gram in step 2
The ratio that 0.05-0.5 grams of poly-aluminium is added in humic acid is added the poly-aluminium solution that concentration is 1-10g/L and preferably plants according to every gram of corruption
The poly-aluminium that concentration is 8g/L is added in the ratio that 0.6 gram of poly-aluminium is added in acid.
Technology explanation: the utilization rate of poly-aluminium is relatively abundant, and humic acid flocculation is more complete.
Embodiment 5
A kind of lignite utilizes method, and the present embodiment and embodiment 1 or 2 or 3 or 4 are essentially identical, the difference is that: in step 2
Humic acid by first pipe (2-10) nozzle enter the second alkali pool (2-11) in the form of flocculate by the second leakage fluid dram (2-13)
The discharge time used is 10-300 minutes, and it is 30 minutes that the time used, which is preferably discharged,.
Technology explanation: it can guarantee within 30 minutes that flocculation is more complete.
Embodiment 6
A kind of lignite utilizes method, and the present embodiment and embodiment 1 or 2 or 3 or 4 or 5 are essentially identical, the difference is that: step 2
In the 6th on-line pH value regulating device (2-30), adjust pH value between 10.5-11.0；The is equipped in third pipeline (2-17)
Two on-line pH value regulating devices (2-23), adjusting pH value is preferably the 6th on-line pH value regulating device between 11.0-11.5
(2-30), adjusting pH value is 11.0；It is equipped with the second on-line pH value regulating device (2-23) in third pipeline (2-17), adjusts pH value
It is 11.0.
PH value is good for 11.0 extraction effects, while can be to avoid the production of meta-aluminate.
Embodiment 7
A kind of lignite utilizes method, and the present embodiment and embodiment 1 or 2 or 3 or 4 or 5 are essentially identical, the difference is that: step 4
According to the molar ratio of hydrochloric acid and aluminium hydroxide be 10:1-5:1 ratio, by aluminium hydroxide be added 4mol/L hydrochloric acid in, preferably
For the ratio for being 10:1 according to the molar ratio of hydrochloric acid and aluminium hydroxide, aluminium hydroxide is added in 4mol/L hydrochloric acid.
It improves hydrochloric acid ratio and helps to improve poly-aluminium quality.
Embodiment 8
A kind of lignite utilizes method, and the present embodiment and embodiment 1 or 2 or 3 or 4 or 5 are essentially identical, the difference is that: step 4
According to the molar ratio of hydrochloric acid and aluminium hydroxide be 10:1-5:1 ratio, by aluminium hydroxide be added 4mol/L hydrochloric acid in, preferably
For the ratio for being 6:1 according to the molar ratio of hydrochloric acid and aluminium hydroxide, aluminium hydroxide is added in 4mol/L hydrochloric acid.
The usage amount of a small amount of aluminium powder can be reduced.
Claims (8)
1. a kind of lignite utilizes method, comprising the following steps:
Step 1: lignite is advanced by No. 1 process chamber to No. 7 process chamber directions, and is spaced a process chamber and material is added；Initial acid
Liquid A1 is advanced from No. 7 process chambers to No. 1 process chamber direction, and one, material interval process chamber is added；Lignite passes through No. n-1 processing
The first grid of room (1-2) enters n process chamber, and acid solution enters n process chamber by the first inlet tube (1-10), in the first agitating paddle
Extracted under (1-6) stirring action, after extraction starting the first grid (1-2) simultaneously acid solution by the first leakage fluid dram (1-3) arrange
N process chamber is entered by the first inlet tube (1-10) again out, forms circulation in acid solution, when lignite passes through the first lattice of n process chamber
After grid (1-2) enter n+1 process chamber, acid solution enters the first gathering tube (1- by the first leakage fluid dram (1-3) in n process chamber
12) enter n-1 process chamber, enter the first centrifuge (1-13) after lignite passes through No. 7 process chambers, solid A after centrifuge separation
Into in the first alkali pool (2-1)；When acid solution pH value is greater than 4, by being labeled as material W, material in the second gathering tube (1-11)
W enters in separate tank processing system (4)；
Step 2: solid A is entered in the first alkali pool (2-1) by feed points (2-19) after centrifuge separation, and lye is in aeration and gravity
Collective effect under, mobile to the second grid (2-2), and realized and be separated by solid-liquid separation by the second grid (2-2), solid is after extracting
Lignite waste residue B, liquid is the second extracting solution C containing humic acid, and the second extracting solution C enters the first surge tank (2-21), when
When extracting solution C volume is the 80% of the first surge tank (2-21), the second extracting solution C enters the second surge tank (2-22), the first buffering
Tank (2-21) sampling carries out flocculation detection, and extracting solution C is put into the second alkali pool (2-11) in the first surge tank (2-21), adds simultaneously
Enter poly-aluminium solution, the molal quantity that poly-aluminium solution is added is to be added the 80% of poly-aluminium molal quantity needed for calculating according to testing result；First
Surge tank (2-21) and the second surge tank (2-22) alternately carry the second extracting solution C, are put into the second alkali pool (2- after sample detection
11) in, while the poly-aluminium solution that concentration is 1-10g/L is added according to the ratio that 0.05-0.5 grams of poly-aluminium is added in every gram of humic acid,
Humic acid by first pipe (2-10) nozzle enter the second alkali pool (2-11) in the form of flocculate by the second leakage fluid dram (2-13)
The discharge time used is 10-300 minutes, is separated by solid-liquid separation after flocculation by the first decanter centrifuge (2-16), and solid is flocculation
Object D, liquid are lye E；Lye E returns to the first alkali pool (2-1) by third pipeline (2-17) and the second inlet tube (2-18), follows
Ring uses, and feed points (2-19) middle side part is equipped with the 6th on-line pH value regulating device (2-30) in the first alkali pool (2-1), adjusts
PH value is between 10.5-11.0；It is equipped with the second on-line pH value regulating device (2-23) in third pipeline (2-17), adjusts pH value
Between 11.0-11.5；
Step 3: flocculate enters in sour cell system (3), in 1-4 second processing room (3-1) pH value of acid solution be respectively 6,4,
2, flocculate is flowed by solution and the 4th grid (3-2) moves, successively from No. 1 second processing room (3-1) to No. 4 second processings
Room (3-1) movement, is centrifugated, and clear water is cleaned to neutrality, alcohol is washed, 80 DEG C of dry 2-6 by the second decanter centrifuge (3-5)
Hour；In No. 4 second processing rooms (3-1) after acid liquor filtering, as acid solution A1 initial in lignite processing system；No. 3 second processings
Enter in No. 4 second processing rooms (3-1) after acid liquor filtering and after concentrated hydrochloric acid mixing in room (3-1), keeps No. 4 second processing rooms
The stabilization of (3-1) pH value and volume；Enter No. n+1 the in n second processing room (3-1) after acid liquor filtering and after concentrated hydrochloric acid mixing
In two process chambers (3-1)；Enter in No. 1 second processing room (3-1) after washing lotion and concentrated hydrochloric acid mixing in washing lotion tank (3-7)；
Acid solution W of the step 4:pH value greater than 4 enters in knockout drum (4-1), adjusts pH=7 of solution, is separated by filtration, and liquid Y is richness
In acid solution；The acid solution in No. 4 second processing rooms (3-1) is added to knockout drum (4-1), until pH value of solution≤3, solution is put into fastly
In fast mixing channel (4-2), solution is in the 4th online pH regulation device (4-21), agitating device (4-22) and ultrasonic mixing device
Under the action of (4-23), after quickly adjusting pH=7, into third process chamber (4-3), by the 5th grid (4-31) by solid hydrogen
Aluminium oxide separation, solution produce the raw material of fulvic acid by being incorporated as after the multiple circulating filtration of the circulatory system with solution Y；
Aluminium hydroxide is added in 4mol/L hydrochloric acid the ratio for being 10:1-5:1 according to the molar ratio of hydrochloric acid and aluminium hydroxide,
110 DEG C stirring 3-5 hours, a small amount of aluminium powder is added to solution no longer vigorous reaction, 90 DEG C of adjusting PH to 4.5, after staticly settling again
Filtering obtains polymeric aluminum chlorides solution, adjusts concentration, and the humic acid that flocculates is added in the second alkali pool (2-11).
2. a kind of lignite utilizes method as described in claim 1, it is characterised in that be added 0.05 according to every gram of humic acid in step 2
The poly-aluminium that concentration is 1g/L is added in the ratio of gram poly-aluminium.
3. a kind of lignite utilizes method as described in claim 1, it is characterised in that be added 0.5 according to every gram of humic acid in step 2
The poly-aluminium that concentration is 10g/L is added in the ratio of gram poly-aluminium.
4. a kind of lignite utilizes method as described in claim 1, it is characterised in that be added 0.6 according to every gram of humic acid in step 2
The poly-aluminium that concentration is 8g/L is added in the ratio of gram poly-aluminium.
5. a kind of lignite utilizes method as claimed in claim 1 or 2 or 3 or 4, it is characterised in that humic acid is by first in step 2
When pipeline (2-10) nozzle enters the second alkali pool (2-11) in the form of flocculate used in the second leakage fluid dram (2-13) discharge
Between be 30 minutes.
6. a kind of lignite utilizes method as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that the 6th is online in step 2
PH value regulating device (2-30), adjusting pH value is 11.0；The second on-line pH value regulating device (2- is equipped in third pipeline (2-17)
23), adjusting pH value is 11.0.
7. a kind of lignite utilizes method as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that in step 4 according to hydrochloric acid with
The molar ratio of aluminium hydroxide is the ratio of 10:1, and aluminium hydroxide is added in 4mol/L hydrochloric acid.
8. a kind of lignite utilizes method as described in claims 1 or 2 or 3 or 4 or 5, it is characterised in that in step 4 according to hydrochloric acid with
The molar ratio of aluminium hydroxide is the ratio of 6:1, and aluminium hydroxide is added in 4mol/L hydrochloric acid.
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| US5004831A (en) * | 1988-11-16 | 1991-04-02 | National Energy Council | Recovery of humic acids |
| CN102558573A (en) * | 2011-12-06 | 2012-07-11 | 中南大学 | Method for extracting high-purity humic acid from low-rank coal |
| CN104987873A (en) * | 2015-05-25 | 2015-10-21 | 昆明理工大学 | Cascade utilization method of inferior lignite |
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2018
- 2018-08-24 CN CN201810970462.4A patent/CN108948374B/en not_active Expired - Fee Related
Patent Citations (4)
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| US5004831A (en) * | 1988-11-16 | 1991-04-02 | National Energy Council | Recovery of humic acids |
| CN102558573A (en) * | 2011-12-06 | 2012-07-11 | 中南大学 | Method for extracting high-purity humic acid from low-rank coal |
| CN104987873A (en) * | 2015-05-25 | 2015-10-21 | 昆明理工大学 | Cascade utilization method of inferior lignite |
| CN105461758A (en) * | 2015-11-18 | 2016-04-06 | 河南理工大学 | A method of increasing a humic acid extraction ratio from brown coal |
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| 王颖 等: "褐煤腐植酸的抽提及其对褐煤吸水性能的影响", 《化学工程》 * |
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